FMPhos: Expanding the Catalytic Capacity of Small-Bite-Angle Bisphosphine Ligands in Regioselective Alkene Hydrofunctionalizations
FMPhos: Expanding the Catalytic Capacity of Small-Bite-Angle Bisphosphine Ligands in Regioselective Alkene Hydrofunctionalizations
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DOI：
10.1021/acscatal.0c04199
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发表时间：
2020-12-18
期刊：
影响因子：
12.9
通讯作者：
Dong, Guangbin
中科院分区：
文献类型：
--
作者：
Chen, Xiao-Yang;Zhou, Xukai;Dong, Guangbin
与过渡金属催化可用的大量大咬角双膦配体相反，小咬角双膦配体的发展受到其单原子骨架上可获得的有限结构变化的影响。在此，我们报告了一种离散的非常小咬角双膦配体，即FMPhos的设计和应用。该配体在单碳连接体上附加了一个芴-亚甲基单元，具有异常坚硬的主链，可能在催化过程中稳定了与过渡金属的络合作用。与已知的dppm配体相比，它在铱和铑催化的烯烃加氢官能化反应中表现出优异的反应活性和区域选择性。
In contrast to the plethora of large-bite-angle bisphosphine ligands available to transition-metal catalysis, the development of small-bite-angle bisphosphine ligands has suffered from the limited structural variations accessible on their single-atom-containing backbones. Herein, we report the design and applications of a discrete very small bite-angle bisphosphine ligand, namely, FMPhos. Featuring a fluorene-methylene unit appended on the single-carbon linker, the ligand harbors an unusually rigid backbone that presumably stabilizes its complexation with transition metals during catalysis. Compared with the known dppm ligand, it exhibited superior reactivity and regioselectivity in a number of alkene hydrofunctionalization reactions, catalyzed by iridium and rhodium.